Low temperature synthesis of aluminum hydr(oxide) inside porous media

ABSTRACT

Preparing a porous hybrid media includes contacting porous media (e.g., strong base ion-exchange media) with an aqueous solution including aluminum ions to yield a aluminum-ion-containing porous media, contacting the aluminum-ion containing porous media with a reducing agent to impregnate elemental aluminum in the porous media, and oxidizing the elemental aluminum to yield a porous hybrid media including aluminum hydr(oxide) impregnated in the porous media. In some cases, a pH of an aqueous mixture including the aluminum-ion-containing porous media may be adjusted to form a floc including aluminum hydroxide, and the aluminum hydroxide-containing porous media may be contacted with a reducing agent to yield a porous hybrid media including aluminum hydr(oxide) impregnated in the porous media. The porous hybrid media may advantageously be prepared at low temperature (e.g., room temperature).

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Application Ser. No. 62/400,923 entitled “LOW TEMPERATURE SYNTHESIS OF ALUMINUM OXIDE INSIDE POROUS MEDIA” and filed on Sep. 28, 2016, which is incorporated by reference herein in its entirety.

STATEMENT OF GOVERNMENT INTEREST

This invention was made with government support under 1449500 awarded by the National Science Foundation. The government has certain rights in the invention.

TECHNICAL FIELD

This invention relates to low temperature synthesis of aluminum hydr(oxide) inside porous media, the resulting hybrid media, and its use for simultaneous removal of multiple contaminants from water.

BACKGROUND

Activated alumina (Al₂O₃) is widely used as a desiccant, catalyst, and selective adsorbent for water and gas contaminants. Al₂O₃ is typically synthesized from gibbsite (Al(OH)₃), or materials containing gibbsite, by slow or flash dihydroxylation at temperatures exceeding 400° C. The resulting Al₂O₃ is in the form of fine mesoporous particles with poor physical integrity, having limited effectiveness in water treatment processes. To facilitate use in fixed bed reactor configurations, Al₂O₃ is usually aggregated in beads. Nevertheless, problems related to adsorbent stability, attrition, surface area decrease, and porosity reduction remain. In addition, the high temperatures typically employed in calcination of aluminum to yield Al₂O₃ limit the feasibility of forming hybrid media including Al₂O₃ by such methods.

SUMMARY

In a first general aspect, preparing a porous hybrid media includes contacting porous media with an aqueous solution including aluminum ions to yield a mixture, adjusting a pH of the mixture to form a floc including aluminum hydroxide, removing liquid from the mixture to yield aluminum hydroxide-containing porous media, and contacting the aluminum hydroxide-containing porous media with a reducing agent to yield a porous hybrid media including aluminum hydr(oxide) impregnated in the porous media.

Implementations of the first general aspect may include one or more of the following features.

The aluminum ions may be derived from aluminum chloride. The reducing agent may include borohydride. Adjusting the pH of the mixture typically includes increasing the pH of the mixture to less than six (e.g., between 4 and 6). Adjusting the pH of the mixture may further include, after increasing the pH of the mixture to less than 6, increasing the pH of the mixture to greater than 6 and less than 8. Preparing the porous hybrid media may occur at room temperature or a temperature less than about 40° C. The porous media may include strong base ion-exchange media. The aluminum content of the porous hybrid media is typically between 3 wt % and 4 wt % of the porous hybrid media. The aluminum hydr(oxide) includes γ-Al₂O₃, amorphous Al₂O₃, amorphous AlO(OH), or a combination thereof.

A second general aspect includes the porous hybrid media prepared by the first general aspect.

In a third general aspect, preparing a porous hybrid media includes contacting porous media with an aqueous solution including aluminum ions to yield a aluminum-ion-containing porous media, contacting the aluminum-ion containing porous media with a reducing agent to impregnate elemental aluminum in the porous media, and oxidizing the elemental aluminum to yield a porous hybrid media including aluminum hydr(oxide) impregnated in the porous media.

Implementations of the third general aspect may include one or more of the following features.

The aluminum ions may be derived from aluminum chloride. The reducing agent may include borohydride. Preparing the porous hybrid media may occur at room temperature or a temperature less than about 40° C. The porous media may include strong base ion-exchange media. The aluminum content of the porous hybrid media is typically between 2 wt % and 3 wt % of the porous hybrid media. The aluminum hydr(oxide) includes γ-Al₂O₃, amorphous Al₂O₃, amorphous AlO(OH), or a combination thereof. Oxidizing the elemental aluminum includes contacting the elemental aluminum with oxygen, such as oxygen in the air or in an aqueous solution.

A fourth general aspect includes the porous hybrid media prepared by the third general aspect.

Advantages include preparation of hybrid media containing aluminum hydr(oxide) at low temperature (e.g., room temperature), thereby avoiding elevated temperatures detrimental to the porous media. The resulting porous hybrid media is able to remove multiple contaminants from water simultaneously, including one or more of weak acid anions (e.g., fluoride and nitrate) and strong acid anions (for porous media including various ion exchange resins), organic contaminants (for porous media including activated carbon), and specific cations and weak acid anions such as fluoride (for porous media including cation exchange resins).

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A and 1B are flowcharts describing processes for low temperature synthesis of aluminum hydr(oxide) inside porous media.

FIG. 2 depicts porous hybrid media described herein.

FIG. 3 shows an X-ray diffraction spectrum of powder aluminum (hydr)oxide formed in strong base ion-exchange media.

FIG. 4 shows BJH differential adsorption pore volume distribution for virgin IX and hybrid Al-HIX media.

FIGS. 5A and 5B show column test breakthrough curves for fluoride removal in simple water matrices expressed as liters treated per kilogram of dry media and aluminum, respectively.

FIGS. 6A and 6B show column test breakthrough curves for fluoride removal in complex water matrices expressed as liters treated per kilogram of dry media and aluminum, respectively.

FIG. 7 shows column test breakthrough curves for sulfate removal in complex water matrices.

FIGS. 8A and 8B show column test breakthrough curves for nitrate removal in simple and complex water matrices, respectively.

FIG. 9 is a graphical illustration of simultaneous removal capacity (SRC) indices; with the dashed line indicating an equimolar capacity for both pollutants. Symbol size is proportional to SRC intensity.

DETAILED DESCRIPTION

A low-temperature method for synthesizing aluminum (hydr)oxide material inside porous media to fabricate porous hybrid media capable of removing nitrate and fluoride from aqueous media, such as contaminated groundwater, is described. As used herein, “aluminum hydr(oxide)” refers to aluminum oxyhydroxide (AlO(OH)), aluminum oxide (Al₂O₃), or both. “Low temperature” generally includes a temperature in a range of 0-40° C., such as room temperature or. In some cases, “low temperature” includes a temperature less than a temperature at which a structure or function of the porous media is deformed or destroyed, respectively. Suitable porous media include strong base ion-exchange resin and weak base ion-exchange resin, activated carbon, siliceous material based media, or other similar porous metal oxide media.

Process 100 for low-temperature synthesis of porous hybrid media is depicted in the flowchart of FIG. 1A. In 102, porous media is contacted with an aqueous solution including aluminum ions to yield a mixture. The porous media may be wet before it is contacted with the aqueous solution including aluminum ions, thereby promoting diffusion of the aluminum ions into the porous media. The wet porous media may be prepared by soaking in water (e.g., ultrapure water) for a length of time (e.g., up to 24 hours) to achieve a desired moisture content (e.g., a maximum moisture content). In some cases, the mixture is agitated (e.g., stirred) for a length of time (e.g., up to 24 hours). The aqueous solution including aluminum ions may be saturated. In general, the resulting aluminum hydr(oxide) content of the porous hybrid media depends on the aluminum ion concentration, with higher aluminum ion concentration yielding higher aluminum hydr(oxide) content. Aluminum ions in the aqueous solution may be derived from salts such as aluminum chloride, aluminum sulfate, aluminum fluoride, aluminum nitrate, or a combination thereof.

In some cases, a pH of the mixture is adjusted to below 6 (e.g., to about 4.5) or above 8 to inhibit floc formation and allow aluminum ions to enter pores in the porous media over a length of time (e.g., up to 24 hours). In 104, a pH of the mixture is adjusted to form a floc including aluminum hydroxide. A floc is typically formed when the pH of the mixture is adjusted to a pH in a range of 6 to 8. The floc “locks” the aluminum inside the pores of the porous media. As used herein, “floc” generally refers to a flocculent mass formed by the aggregation of suspended particles. The pH of the mixture may be adjusted by adding an aqueous solution of a base. Examples of suitable bases include sodium hydroxide, potassium hydroxide, and the like.

In 106, liquid is removed from the mixture to yield aluminum hydroxide-containing porous media. In 108, the aluminum hydroxide-containing porous media is contacted with a reducing agent to yield a porous hybrid media including aluminum hydr(oxide) impregnated in the porous media. The reducing agent is typically in an aqueous solution. Suitable reducing agents include NaBH₄, LiBH₄NaAlH₄, KAlH₄, and the like. The aluminum content of the porous hybrid media is typically at least 3 wt % (e.g., between 3 wt % and 5 wt %, or between 3 wt % and 4 wt %) of the porous hybrid media. At least some of the aluminum hydr(oxide) may be in the form of nanoparticles. In some cases, the aluminum hydr(oxide) includes γ-Al₂O₃, amorphous Al₂O₃, AlO(OH), or a combination thereof. The resulting porous hybrid media may be washed with water to achieve a neutral pH (e.g., a pH above 4.5, or about 7). In some cases, the porous hybrid media is stored under water after washing.

Process 110 for low-temperature synthesis of porous hybrid media is depicted in the flowchart of FIG. 1B. In 112, porous media is contacted with an aqueous solution including aluminum ions to yield an aluminum-ion-containing porous media. The porous media may be wet before it is contacted with the aqueous solution including aluminum ions, thereby promoting diffusion of the aluminum ions through pores in the porous media. The wet porous media may be prepared by soaking in water (e.g., ultrapure water) for a length of time (e.g., up to 24 hours) to achieve a desired moisture content (e.g., a maximum moisture content). In some cases, the wet porous media and the aqueous solution including aluminum ions are agitated (e.g., stirred) for a length of time (e.g., up to 24 hours). The aqueous solution including aluminum ions may be saturated. In general, the resulting aluminum hydr(oxide) content in the porous hybrid media depends on the aluminum ion concentration, with higher aluminum ion concentration yielding higher aluminum hydr(oxide) content. Aluminum ions in the aqueous solution may be derived from salts such as aluminum chloride, aluminum sulfate, aluminum fluoride, aluminum nitrate, or a combination thereof.

In 114, the aluminum-ion containing porous media is contacted with a reducing agent to impregnate elemental aluminum in the porous media. The reducing agent is typically in an aqueous solution. Suitable reducing agents include NaBH₄, LiBH₄NaAlH₄, KAlH₄, and the like.

In 116, the elemental aluminum is oxidized to yield a porous hybrid media including aluminum hydr(oxide) impregnated in the porous media. Oxidizing the elemental aluminum includes contacting the elemental aluminum with oxygen. The oxygen is typically environmental oxygen, such as oxygen in the air or oxygen dissolved in water or an aqueous solution. The aluminum content of the porous hybrid media is at least 2 wt % (e.g., between 2 wt % and 4 wt %, or between 2 wt % and 3 wt %) of the porous hybrid media. At least some of the aluminum hydr(oxide) may be in the form of nanoparticles. In some cases, the aluminum hydr(oxide) includes γ-Al₂O₃, amorphous Al₂O₃, or a combination thereof. The resulting porous hybrid media may be washed with water to achieve a neutral pH (e.g., a pH above 4.5, or about 7). In some cases, the porous hybrid media is stored under water after washing.

In some cases, metal salts, such as titanium salts, are introduced into the porous hybrid media to yield improved sorbent properties or selectivity for specific contaminants. Porous hybrid media described herein may be used in fixed bed reactor configurations for small treatment systems, such as household treatment systems.

FIG. 2 depicts porous hybrid media particle 200 defining a multiplicity of pores. Some pores in porous hybrid media particle 200 are impregnated with aluminum hydr(oxide) 202. At least some of the aluminum hydr(oxide) may be in the form of nanoparticles. Some pores in porous hybrid media particle 200 may include quaternary amines 204. Quaternary amines 204 may restrict access to larger oxyanions (e.g., nitrate and sulfate), while still allowing for ion exchange of smaller anions, such as fluoride. Some pores in porous hybrid media particle 200 may include chloride 206. Nitrate 208 and fluoride 210 may diffuse into porous hybrid media particle 200, displacing chloride 206. Aluminum (hydr)oxide 202 also functions as a sorbent for the fluoride ions. With an increase in aluminum content in porous hybrid media particle 200, the number of available sorption sites increases, improving fluoride sorption capacity and also accommodating co-contaminant removal.

Example

Aluminum (hydr)oxide was synthesized at a room temperature by reducing aluminum ion precursor with sodium borohydride in ultrapure water. To ensure complete reduction of the aluminum, borohydride was provided in excess of the stoichiometric requirements. The same process was employed to synthesize aluminum (hydr)oxide inside the pores of commercially-available nitrate selective strong base ion-exchange (IX) resin (Purolite A520E).

Before the modification with aluminum (hydr)oxide, the virgin ion-exchange media was soaked in water to expand the resin, open its macropores, and improve diffusion of the aluminum ions. The excess water was then decanted, and 100 g of wet resin was mixed with a saturated solution of the aluminum salt precursor, prepared by dissolving 55 g of AlCl₃×6H₂O in 50 mL of water. The aluminum cations, with free liquid diffusivity of D₁=5.41×10⁻⁶ cm² s⁻¹ in water at 25° C., diffuse into the pores and establish equilibrium with the bulk within minutes to hours of creating a high concentration gradient. Nonetheless, to ensure comprehensive diffusion of the aluminum ions inside the pores, the ion-exchange media and aluminum solution were gently mixed for 1 day. The ion-exchange resin primed with aluminum ions was then divided equally into two portions, and two synthesis approaches were undertaken to fabricate two different types of aluminum (hydr)oxide hybrid media.

In the first synthesis approach, as described with respect to FIG. 1B, the excess aluminum solution was decanted and the aluminum ions inside the pores of the primed resin were reduced by adding 50 mL solution containing 10 g of NaBH₄. In the second synthesis approach, as described with respect to FIG. 1A, the aluminum ion primed resin was contacted with NaOH until stable white Al(OH)₃ floc formed (pH>4.5). The underlying premise for this step was to form large floc inside the resin macropores to minimize aluminum leaching from the resin during the subsequent reduction step and consequently contribute to higher aluminum (hydr)oxide content in the hybrid media. Upon stable floc formation, the media was left to equilibrate for 1 day and ensure stable floc and pH before the excess floc was decanted and 50 mL of the NaBH₄ solution were introduced to reduce the trapped aluminum. In both synthesis approaches, the media was gently mixed with the reducing agent for 2 h before rinsing the hybrid media with ultrapure water until the decanted solution exhibited pH˜7. Both media were stored in ultrapure water before characterization and use. The hybrid media synthesized via the first approach was termed Al-HIX-2, while its counterpart hybrid media was termed Al-HIX-4.

High resolution X-ray diffraction (XRD) analysis (PANalytical X'Pert Pro, CuKα source) was employed to confirm aluminum (hydr)oxide formation and determine the presence of crystalline phases and structural characteristics. Focused ion beam and scanning electron microscopy (FIB/SEM) techniques (Nova 200 NanoLab UHR FEG-SEM/FIB and XL 30 by FEI) were used to determine the size and shape of the aluminum (hydr)oxide material deposited within the pores of both hybrid (Al-HIX) media. The aluminum distribution throughout the hybrid Al-HIX media was evaluated by energy dispersive X-ray (EDS) elemental mapping. The FIB/SEM and EDS analyses were also performed on the untreated IX resin, which served as a baseline for comparison with the hybrid media.

Gravimetric analysis at 700° C. was employed to determine the aluminum content of the Al-HIX media and confirm the absence of aluminum in the untreated IX resin. Particle densities and porosities of the Al-HIX and IX resins, and conventional activated alumina (AA) (AA-400G, 28×48 mesh, Alcan) were determined via pycnometer analysis. For Al-HIX and IX resins, specific surface area was determined via the Brunauer-Emmet-Teller (BET) method, and their pore size distribution was obtained via the Barret-Joyner-Halenda (BJH) method using MicroMeritics Tristar-II 3020 automated gas adsorption analyzer within the working range of the instrument (from 1.7 to 300 nm).

The iso-electric point (pH_(PZC)) was determined via pH drift method after 3 days equilibration in 10 mM KCl background electrolyte solution. For porous and large media that require longer time for equilibration, this method can be advantageous compared to titration or electrophoresis methods.

To gain insight into the density of aluminum sites created in the hybrid Al-HIX media, the change in concentration of protons resulting from aluminum (hydr)oxide impregnation inside the ion-exchange media was calculated and normalized per dry weight and surface area of Al-HIX-2 and Al-HIX-4 media. The difference in iso-electric points of the hybrid and virgin media was used to estimate the generation of new positive sites, and BET data was utilized for the specific surface area.

Short-bed column (SBC) tests with sufficient bed depth to capture the entire mass transfer zone when operated at hydraulic loading rates of full-scale systems were used to assess contaminant removal performance of all media under continuous-flow conditions. The SBC tests were conducted in glass columns (d_(Column)=1.5 cm) packed with ˜14.6 cm of media. The realistic hydraulic loading rate of 1.52 L s⁻¹ m⁻² (2.22 gal min⁻¹ ft⁻²) was applied, which enabled capturing the mass transfer zones for both contaminants at an empty bed contact time (EBCT) of 1.6 min.

The continuous-flow column tests were conducted with fluoride and nitrate as model contaminants to estimate each media's contaminant removal performance. The continuous-flow tests were conducted in two water matrices: (1) a simple matrix consisting of nitrate and fluoride in ultrapure water buffered with 10 mM NaHCO₃; and (2) a complex matrix of NSF 53 challenge water that simulates realistic and challenging groundwater conditions (NSF/ANS, 2007). Both water matrices were spiked with 12 mg (F) L⁻¹ and 20 mg (NO₃—N) L⁻¹, which represent realistic conditions exceeding the MCLs for these contaminants. The pH was corrected with HCl to realistic conditions (pH_(FINAL)=7.1±0.1). Fluoride and nitrate concentrations were analyzed using an ion chromatography instrument (Thermo scientific, Dionex ICS-1100).

The contaminant removal performance of conventional activated alumina was also tested under the same conditions to compare the performance of the newly fabricated Al-HIX media with commercially available BAT for fluoride removal. Additionally, to closely evaluate the effect of aluminum on fluoride sorption, breakthrough curves of Al-HIX-2, Al-HIX-4, and AA media were normalized per aluminum content.

For both fluoride and nitrate, the contaminant removal performance at 95% (q₉₅%) breakthrough (C_(eff)/C₀=0.95), which is considered complete contaminant breakthrough from an operational perspective, was estimated via Eq. (1):

$\begin{matrix} {q_{95\%} = \frac{Q \times {\int_{0}^{t}{{C(t)}{dt}}}}{m}} & (1) \end{matrix}$

where q₉₅% is the sorption capacity of the dry media (mg g⁻¹), Q is the flowrate in the packed-bed (L min⁻¹), C(t) is the difference between the initial and effluent sorbate concentrations (mg L⁻¹) at time t (min), and m is the mass of the dry sorbent media used in the packed-bed column (g dry media).

Comparison of the media performance for simultaneous removal of two contaminants was conducted by estimating the Simultaneous Removal Capacity (SRC) index as summarized in Eq. (2):

SRC=(Combined Capacity)×(Weighting Factor)  (2)

where Combined Capacity represents an average of the removal capacities (q) for each individual pollutant as defined in Eq. (3):

Combined Capacity=√{square root over (q(F)² +q(NO₃—N)²)}  (3)

and Weighting Factor is a component that attributes higher scores to media with similar removal capacity for both pollutants over sorbents with preferential removal capacity (Eq. (4)):

$\begin{matrix} {{{Weighting}\mspace{14mu} {Factor}} = {\sin \left( {2 \times \tan^{- 1}\frac{q(F)}{q\left( {{NO}_{3} - N} \right)}} \right)}} & (4) \end{matrix}$

Considering that simple water matrix does not account for reduced performance as a result of competing ions, which are only present in realistic water matrices, the SRC was estimated only for the q₉₅% obtained with the complex water matrix.

FIG. 3 shows an X-ray diffraction (XRD) spectrum of powder aluminum (hydr)oxide, suggesting that a mix of γ-Al₂O₃ and amorphous aluminum (hydr)oxide can be obtained by reducing aluminum ion precursors with borohydride, followed by exposure to environmental oxygen. The broad diffraction lines, which typically stem from lattice distortions or defects and are generally attributed to amorphous phase of obtained media, prevented quantification of each phase. Although it is likely that the formed aluminum material contains amorphous AlOOH, it is unlikely that any Al(OH)₃ (s) is present because the obtained material remained stable at pH˜3 and pH>12.

The synthesized powder aluminum (hydr)oxide material exhibited an iso-electric point of pH_(PZC)˜8.5. This value corresponds well with the pH_(PZC)˜8 measured for the commercial activated alumina used in this experiment and reported values reported for γ-Al₂O₃, which range between 8 and 9. The higher iso-electric point of the aluminum (hydr)oxide material contributed to the overall iso-electric point of the hybrid media, which increased from pH_(PZC)˜4.7 to pH_(PZC)˜5.3 for the virgin ion-exchange and hybrid media, respectively. As summarized in Table 1, the iso-electric point was the same for both hybrid media, although Al-HIX-4, which was fabricated via the second synthesis approach, exhibited almost twice as much aluminum than the Al-HIX-2.

TABLE 1 Aluminum content, pore properties, specific surface area, and point of zero charge of tested media Al Content Particle Bulk density^(a) BET surface area Pore volume Media (%) porosity ϵ_(P)(%) (g L⁻¹) (m² g⁻¹) (cm³ g⁻¹) pH_(PZC) IX 0.00 77 377.6  7.15 0.016^(b) 4.7 Al-HIX-2 2.12 72 386.4 23.09 0.047^(b) 5.3 Al-HIX-4 3.70 64 398.3 14.97 0.027^(b) 5.3 AA 52.91 78 808.3 237^(c)   0.33^(c) 8.0 ^(a)Expressed per dry media ^(b)BJH Desorption cumulative volume of pores between 1.7 nm and 300 nm width ^(c)Hao, J., Han, M.-J., Meng, X., 2009. Preparation and evaluation of thiol-functionalized activated alumina for arsenite removal from water. J. Haz. Mat. 167, 1215-1221.

The increase in pH_(PZC) due to impregnation of IX with aluminum (hydr)oxide consequently resulted in increasing of net positive surface charge of hybrid Al-HIX media for 4 times. The ˜3.7% Al in Al-HIX-4 yielded ˜13.08 μmol m⁻² of new positive surface charges, while the ˜2.1% Al in Al-HIX-2 yielded ˜9.45 μmol m⁻². The estimated higher increase in net positive surface charge density of the Al-HIX-4, when compared to its Al-HIX-2 counterpart, stemmed from lower surface area of the Al-HIX-4 media and was insufficient to cause any differentiating change in the iso-electric point. As summarized in Table 1, surface area increased almost three-fold with the introduction of ˜2.1% aluminum in Al-HIX-2 compared to virgin IX resin. This could be attributed to new surface area generated by the aluminum (hydr)oxide inside the pores of the media. Interestingly, increasing aluminum from ˜2.1% to ˜3.7% decreased the specific surface area, but the specific surface area of Al-HIX-4 remained larger than the virgin IX media. In contrast, the reported specific surface area of activated alumina (AA) is significantly higher (Table 1).

The gain in the specific surface area of both hybrid media due to the increase in aluminum content reduced particle porosity. The particle porosity of the media decreased from ε_(P)≈77% for the virgin IX to ε_(P)≈72% and ε_(P)≈64% for the Al-HIX-2 and Al-HIX-4 media, respectively. These values are comparable with particle porosity for activated alumina of ε_(P)≈78%.

The cumulative pore volume also followed the trend exhibited by the media's specific surface area. According to the BJH model analysis, which is summarized in Table 1, the cumulative pore volume between 1.7 nm and 300 nm initially increased from 0.016 cm³ g⁻¹ to 0.047 cm³ g⁻¹ with the increase in aluminum content to ˜2.1%, and then it decreased to 0.027 cm³ g⁻¹ when aluminum content increased to ˜3.7%. This corresponds well with the specific surface area trend because the majority of the new pore volume is created in a mesoporous region below 20 nm, which is the main contributor of high surface area together with the microporous region. Interestingly, it is not only the <20 nm region that is characterized by greater pore volume, but the entire region <300 nm exhibited increases in the respective cumulative pore volumes by a factor of 2 to 3. FIG. 4 shows BJH differential adsorption pore volume for virgin IX and hybrid Al-HIX media. As illustrated in FIG. 4, it could be postulated that the resin macropore volume for d_(Pore)>300 nm is probably being reduced by the aluminum (hydr)oxide deposition to the benefit of new surface area and volume formation in the mesopore and low macropore regions.

The changes in pore volume and surface were not readily observed with the SEM technique. Discrete nanoparticles of aluminum (hydr)oxide could not be identified by the backscatter detector because of relatively small differences in atomic masses between the low atomic mass elements (carbon, nitrogen, and oxygen) in the polymer resin and the aluminum. However, as the aluminum content increased, smoothing of the surfaces within the pores ion-exchange media was observed, which could be attributed to the formation of aluminum (hydr)oxide nano-films. This pore morphology trend was observed throughout the entire depth of the examined media, suggesting the even distribution of the aluminum inside the resin particles, which was confirmed by energy dispersive X-ray elemental mapping microanalysis.

FIGS. 5A and 5B illustrate breakthrough curves for fluoride removal by the activated alumina and both the virgin and hybrid ion-exchange types of media in a simple water matrix (i.e., no competing ions). As depicted in FIG. 5A, ˜45 L of water could be treated per kilogram of dry virgin IX media until the column reached 95% exhaustion. The addition of 2.1% aluminum as aluminum (hydr)oxide into the pores of the IX media (Al-HIX-2) significantly improved the fluoride removal as this media was able to treat ˜200 L of water per kilogram of dry media before 95% breakthrough was reached. The fluoride removal performance of the media slightly decreased with increase in aluminum content from 2.1% to 3.7%. As illustrated in FIG. 5A, the Al-HIX-4 was able to treat ˜130 L of simple water per kilogram of dry media until fluoride breakthrough exhibited 95%. Although both Al-HIX media performed the same until 50% breakthrough was reached, it appears that the lower particle porosity of the Al-HIX-4 media may have contributed to a mass-transport induced decrease in this media's performance. As illustrated by the shapes of the Al-HIX curves above 70% breakthrough, faster fluoride intraparticle mass transport was exhibited by the Al-HIX-2. Considering changes in media properties induced by aluminum content shown in Table 1, it can be suspected that lowering the particle porosity and the subsequent increase of media tortuosity dominantly reduced pore diffusivity of fluoride.

The commercially-available activated alumina media outperformed the Al-HIX media for fluoride removal by a factor of >10. When normalized on basis of mass dry media, a kilogram of activated alumina was able to treat ˜2,000 L of fluoride from simple matrix until 95% breakthrough was achieved. This is not surprising considering that activated alumina has a much higher content of aluminum per unit dry media. When the breakthrough curves were compared on basis of volume of water treated per mass of aluminum in the media, the performance trend reversed. The activated alumina removed slightly less fluoride than the two Al-HIX hybrid media. As illustrated in FIG. 5B, activated alumina could treat ˜3,500 L of simple water matrix water per kilogram of Al, which was lower than, but comparable to, the performance of the Al-HIX-4 media. In contrast, the Al-HIX-2 media could treat ˜10,000 L of simple water per kilogram of Al, which implies better utilization of the aluminum (hydr)oxide surface for removal of fluoride than activated alumina.

The presence of co-competing ions in the complex matrix had a differentiating effect on the fluoride removal performance of Al-HIX media. The extent of co-competing ions influence on media performance in continuous-flow system is directly related to ionic: (1) affinity toward media's active sites; (2) concentration; and (3) size. Therefore, it is believed that in the presence of co-competing ions, due to selectivity issues, target contaminant removal decreases. This trend was observed where fluoride removal performance of the Al-HIX-2 media decreased from ˜200 L/kg of dry media for simple water to ˜65 L/kg of dry media for the complex water matrix before 95% breakthrough was observed. The fluoride removal performance of Al-HIX-4 exhibited an opposite trend and was enhanced by the presence of co-contaminants in the complex water matrix. Specifically, this media was able to treat ˜190 L of complex water matrix per kilogram of dry media until 95% of fluoride breakthrough was achieved, which represented an increase of 60 L/kg of dry media as illustrated in FIG. 6A. Virgin IX media, on the other hand, retained fluoride removal of 45 L/kg of dry media even in the complex water matrix. This unexpected trend may be explained by quaternary amines in IX media, which may be in pores that restrict access to larger oxyanions (e.g., nitrate and sulfate), are still available for fluoride ion-exchanging to occur. Although the sum of ionic radius and hydrated shell width of fluoride, nitrate, and sulfate are close to each other (0.212, 0.223 and 0.273 nm, respectively), the difference can be a limiting factor for its diffusion in micro and small mesopores. As small amounts of aluminum (hydr)oxide are introduced, these inaccessible ion-exchange groups may be masked by the aluminum (hydr)oxide, which becomes the main sorbent for the fluoride ions, but it does not provide sufficiently large sorption capacity in presence of competing ions. With an increase in aluminum content, the number of available sorption sites increases significantly, improving fluoride sorption capacity and also accommodating co-contaminant removal, as shown in FIG. 6B.

Based on FIG. 7, which shows that activated alumina has the ability to partially remove sulfate from complex water matrix in addition to fluoride, it could be postulated that sulfate (C_(o)˜50 mg L⁻¹) may partially compete with fluoride for some of the aluminum (hydr)oxide sites. For strong base virgin ion-exchange resin, sulfate removal is expected because the quaternary amine ion-exchange groups are especially designed and positioned to remove strong acid oxyanions. However, sulfate removal increased with addition of aluminum (hydr)oxide content as shown in FIG. 7. The Al-HIX-2, exhibited slightly higher sulfate removal performance than its Al-HIX-4 counterpart. This trend further supports the conjecture that low aluminum (hydr)oxide contents may primarily mask the quaternary amine groups that are generally available only to fluoride. Any additional increase of aluminum (hydr)oxide content, however, appears to mitigate this effect by taking over the fluoride removal pathway.

As illustrated in FIGS. 8A and 8B, activated alumina did not remove nitrate in either water matrix. However, the addition of aluminum (hydr)oxide appears to increase the performance of the ion-exchange media as illustrated in FIG. 8A for the simple water matrix. Strong base ion-exchange resin was able to remove nitrate from ˜1,600 L of simple water per kilogram of dry media until 95% of NO₃—N breakthrough was reached. With addition of 2.1% and 3.7% of aluminum (hydr)oxide inside the pores of the media, these values increased to 1,900 L and 2,600 L/kg of dry media, respectively. This improved performance could be attributed to two factors: (1) modification of the steric effects (i.e., minimization of steric effect influence); and (2) increase in positive surface charge, which reduces the electrostatic repulsion between the surface and oxyanion. This effect appears to be suppressed by the competing ions, which are present in the complex water matrix. As illustrated in FIG. 8B, the nitrate removal breakthrough curves of all ion-exchange media appear to be almost identical. This could be attributed to the presence of sulfate, which competes with nitrate for the available ion-exchange sites. As illustrated in FIG. 7, the effect associated with improved removal of nitrate in simple water appears to be manifested for the sulfate, suggesting that sulfate's greater affinity for the ion-exchange sites over nitrate may be the underlying cause for this behavior.

FIG. 9 illustrates the relation between single sorption capacity calculated from column tests at C_(eff)/C_(o)=95% saturation in complex water matrix. For fluoride removal, the media capacity follows an expected trend, which is closely associated with the aluminum content. For nitrate removal, there was no significant difference between virgin IX or Al-HIX hybrid media, but AA did not exhibit almost any nitrate removal abilities. Further calculation of combined capacity and weighting factor led to SRC indices summarized in Table 2. The Al-HIX-4 media exhibited the highest SRC index that was more than 2 times higher than the one for Al-HIX-2. This suggests that Al-HIX-4 may be more suitable for hybrid sorbent packed-bed configurations in groundwater that resembles similar water chemistry as the complex water matrix used in this study.

TABLE 2 Sorbents ranking based on SRC indices for maximum single sorption capacity values estimated in column tests at C_(eff)/C_(o) = 95% for complex water matrix q_(95%) (μmol q_(95%) (μmol Weight- F g⁻¹ NO₃—N g⁻¹ Combined ing SRC Media dry media) dry media) capacity factor (μmol g⁻¹) IX 11.81 1,721.40 1721.44 0.014 23.62 Al-HIX-2 16.22 1,752.90 1752.98 0.019 32.44 Al-HIX-4 38.56 1,674.80 1675.24 0.046 77.10 AA 327.55 3.70 327.57 0.023 7.40

A number of embodiments have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the disclosure. Accordingly, other embodiments are within the scope of the following claims. 

What is claimed is:
 1. A method of preparing a porous hybrid media, the method comprising: contacting porous media with an aqueous solution comprising aluminum ions to yield a mixture; adjusting a pH of the mixture to form a floc comprising aluminum hydroxide; removing liquid from the mixture to yield aluminum hydroxide-containing porous media; contacting the aluminum hydroxide-containing porous media with a reducing agent to yield a porous hybrid media comprising aluminum hydr(oxide) impregnated in the porous media.
 2. The method of claim 1, wherein the aluminum ions are derived from aluminum chloride.
 3. The method of claim 1, wherein the reducing agent comprises borohydride.
 4. The method of claim 1, wherein adjusting the pH of the mixture comprises increasing the pH of the mixture to less than
 6. 5. The method of claim 4, wherein adjusting the pH of the mixture further comprises, after increasing the pH of the mixture to less than 6, increasing the pH of the mixture to greater than 6 and less than
 8. 6. The method of claim 1, wherein preparing the porous hybrid media occurs at room temperature or a temperature less than about 40° C.
 7. The method of claim 1, the porous media comprises strong base ion-exchange media.
 8. The method of claim 1, wherein an aluminum content of the porous hybrid media is between 3 wt % and 4 wt %.
 9. The method of claim 1, wherein the aluminum hydr(oxide) comprises γ-Al₂O₃, amorphous Al₂O₃, amorphous AlO(OH), or a combination thereof.
 10. The porous hybrid media prepared by the method of claim
 1. 11. A method of preparing a porous hybrid media, the method comprising: contacting porous media with an aqueous solution comprising aluminum ions to yield a aluminum-ion-containing porous media; contacting the aluminum-ion containing porous media with a reducing agent to impregnate elemental aluminum in the porous media; and oxidizing the elemental aluminum to yield a porous hybrid media comprising aluminum hydr(oxide) impregnated in the porous media.
 12. The method of claim 11, wherein the aluminum ions are derived from aluminum chloride.
 13. The method of claim 11, wherein the reducing agent comprises borohydride.
 14. The method of claim 11, wherein preparing the porous hybrid media occurs at room temperature or a temperature less than about 40° C.
 15. The method of claim 11, wherein the porous media comprises strong base ion-exchange medias.
 16. The method of claim 11, wherein an aluminum content of the porous hybrid media is between 2 wt % and 3 wt %.
 17. The method of claim 11, wherein the aluminum hydr(oxide) comprises γ-Al₂O₃, amorphous Al₂O₃, or a combination thereof.
 18. The method of claim 11, wherein oxidizing the elemental aluminum comprises contacting the elemental aluminum with oxygen.
 19. The method of claim 18, wherein contacting the elemental aluminum with oxygen comprises contacting the elemental aluminum with air.
 20. The porous hybrid media prepared by the method of claim
 11. 